Process of desulfurizing petroleum-oils.



. E. B. COBB.

PROCESS 0F DEsULFumzlNG PETROLEUM ons.

APPLICATION FILED SEPT. 1l |915.

2 SHEETS-SHEET l @uw fQ/UJ E. B. COBB.

PROCESS 0E nEsuLEumzlNG PETROLEUM ons.

. APPLICATION FILED SEPI'I 1I 1915- 11193 A si@ Patented Apr. 15, 1919.

2 SHEETS-SHEET 2.

- of elementary sulfur frompetroleum oils. .By elementary sulfur I mean that sulfur ERNEST E. coBE, or' JERSEY CITY, NEWJERSEY, AssIGNoR To STANDARD oIL COMPANY f A CORPORATION oF NEW JERSEY. f

PROCESS F DESULFURIZING PETROLEUM-OILS.

To all whom it may concern:

Be it known that I, ERNEST B. COBB, a

citizen of the United States, residing at Jer- Vfi sey City,'in the county of Hudson and State of New Jersey, have invented certain new and useful Improvements in Processes of Desulfurizing P vtroleum-Oils, ot which the following is a specification.

My invention relates to new and useful improvements in processes for the removal which exists inthe oil in its' elementary forms, such as brimstone, -flowers of sulfur and all other modifications of elementary sulfur heldin physical solution in the oil. 'I he invention is applicable to and covers the removal of elementary sulfur 'primarily existing assuch in the 'oil, and also elementary sirlfur resulting from acid treatment jof the oils and. other processes of relining and chemical treatment. The presence of elementary sulfur in petroleum oils may be as-` certained by first testing the oil by-any of the well-known tests for sulfureted lhydrogen (HZS) and removing'the same` if any be present by any ofthewellknown `processes for this purpose, after'l which a piece of bright copper or silver is'immersedT in the oil freedof 'sulfureted hydrogen (HZS) and Athe oil heated; if any elementarysulfuris present itwill act to tarnish or blanken the copper or silver. The removal of. sulfureted hydrogenfrom the test oil is a necessary preliminary because 1t also darkens A'copper `and silver. But in the treatment 'of the main bodyl of o1l, as hereinafter described,

itis [unnecessary .to remove the -sulfureted hydrogen by preliminary-treatment. l' i I have` discovered that elementary sulfur existing in petroleum oils, either primarily,

with otherI compounds, or elements, may be l v "tho'ugh not necessarily, or by waygof limitation, to monosulfids-:that is 'to say, for example, sodiumsuliid (NaziS), calcium suld (CaS),etc.

jIt is well known that higher sulds of Specication of Letters lfatent.k

Patented Apr. 15,1919.. Application m'ed september 11, 1915.y serialNo. 50,177,

these metals, such as sodium andl calcium, l

exist, andthe chemical action in using sulds thereof, as contemplated by my invention, is to cause removal of the elementary sulfur apparently by simple addition, the sulfur combining with the low sulid of the .alkali metal or alkaline earth metal to produce higher sulfide. It sometimes occurs that the oil Amay contain suliuretedA hydrogen in addition'to elementary sulfur, in which case the addition of an alkali metal or an alkaline earth metal in the form vof the hydroxid will iirst form monosulfid with the Sulureted hydrogen, andthe. monosulid thus `formed, willremove the elementary sulfur. l

My invention, therefore, contemplates the treatment of the oil with an alkali metal i701.. suld or sulfds of the -alkaline earth metals Y' whether the sulfld is applied to the oil.in' l* that form, 'or is formed by adding to `the oil the alkali'metalsor alkaline earth metals and permitting the s ame to react with sul fureted hydrogen exlsting primarilyin, orl

injected into the oil, to form the'sulid of the alkali metal or alkaline earth metal. l

Inreferring to alkali suliid` I include i and the individual preference, but, to a large extent, the alkali'metal sulfide and' thesuliids of the 'alkaline Vearth metals are'fin.-

' telchangeable.; -By suliids ,of .the alkalineor as the result of treatments or reactions q earth metals I mean sulfide, of the .alkaline earth metal group, butin practice I preferably use sulids of lime, although I do not necessarily exclude any of the sulds of the' two groups contemplated. By alkaline sul-` fidas used herein and inthe appended claims, I include the-sulids of the alkali metal group andthe' alkaline earth metal group.

`The invention Ais capable of being praci tised by a variety of apparatus, but, in the aocompanving drawings, have illustrated two types of apparatus which have been successfully used by me.

Figure .l of the drawings is a view in elevationpartly in section of'one type of apparats particularly useful 'in the practice of the invention when employing suliids of the alkali metal group.

' Fig. 2isa View in side elevation of a type of apparatus useful in the practice of the invention when employing sulfids of the all kaliearth group.

` Flg' 3 iS an enlarged detail section lthrough the bottom portion of the apparatus shown in Fig. 2. I will first describe the apparatus illustrated in Figgl ofthe drawings, and then y the method of desulfurizing' carried `out] L thereby, after which I will describe the apparatusof Figs. `2 and 3' and the method performedthereby.V l

Referring particularly to Fig. 1: `i l1 designates a cylinder or receptacle adapted to receive the oil to be treated, and havingl a conical bottom 2 and a ldomeshaped top or cover 3. The conical shaped 1 outlet pipe 7 with the inlet side of a circulating pump 8, said pipe containing a valve 9 'for cutting ofi' and establishing low through the same to the pump. Connected to the outlet side of the pump is a feed pipe 10 extending upward from the umpand provided with a horizontal ortion 11 enterin vide at its end within the cylinder, with a depending pipe 12 vhaving' its lower end closed, but'its sides perforated so as'to dis-` tribute'the chemical in finestreams within the cylinder to insure proper admixture of the samewith'the oil-contentsof the cylinder. .Theppipe 7 is connected at a oint be vtween the valve 9 and the inlet of t e pump' to one end of' a pipe 13, the opposite end of which is connected 1to the pipe 4 at a Vpoint above the valve 5, heretofore mentioned. The ^pipe 13 is provided with controlling valves 13, 14 by means of which communication throughl said pipe 1-3 to the pump is controlled. Connected at Aone end to the pipe 4 between the valve 5 and the point of connection ofy the ipe y13 is an outlet or drain pipe 15 provlded with an outlet neck 16 discharging into the tank 6, heretofore described. The pipe 15 is provided with a controlling valve 17 for controllingfflow therethrough.

- of treating t the side of the cylin er 1 and .pro-

18 designates -a steam inlet pipe entering throughl the dome 3 and provided with a def outlet portion 19` by means of .v

pendin which ive steam may be admitted .to the interior of the cylinder, an air inlet'pipe 20 being connected with pipe 18'and provided with a valve 21 fora 'purpose to be presently described. The pipel 18 may be provided with a valve 22 l lfor controlling the flow of the steam toI thesame to the interior of the cylinder, said pipe 20 being connected with 'the pipe 18 between the valve r 22 and the outlet end of said pipe 18.- Also connected to the steam ,pipe 18 is-a pipe23` leadin to a closed heating coil 24, of any suitab e form, located within the `bottom portion ofthe cylinder, said coil being ro- -vided with a control valve 25 for control ing the` flow therethrough.I The outlet end of the steam coil is shown at-26. I v v The inlet vpipe `for feeding the oil to "be treated, to the cylinder, is shown at 27, the

said Apipe entering the cylinder adj acentthe upper 'portion thereof andl extending to a point preferablyl Within the area of the the lowermos't portion, of the cone-shaped bOttOIIl. Y"

I do not desire` to be insure an adequate understanding of the process embodying my invention.

I will now proceed` to describe the process being'particularly applicable, but not neces,-

fsarily confined, .to parain waXLkerosene oil, and white parailin roil for medicinal use, and I will describe the invention for the sake ofillustration for the removal of elementary sulfur A.from partially, finished white medicinal oil.,

'cone-.shaped bottom. The treated oil may be withdrawn from the cylinder'through yan outlet pipe 28, controlled by a valve 29, said pipe being, located adjacent to, but above,

limited in any way to an apparatus' such as described,.having only describedthe sam@ in detail so as to n e petroleum oilsy with sulfidsv 'of thepalkali metal group, this treatment `rPrevious to treatment this oil may con-i tain .03 er cent. sulfur, of which .02 per cent. is e ementary sulfur and .01 per cent. is in the formV of inodorous sulfur, not elementary, and in thisv form unobjectionable l in oils forthe usestated and-contained in sulfur compounds left after treatment with sulfuric acid, vsaid loil being pumpedfinto the vessel or cylinderl through the pipe 27. When a sufficient amount of the oil has been 'charged intoI the receptacle l-for instance,

impractical `operations I have treatedl 100 barrels of 50 gallons each, when about twothirds full-'steam isadmitted 'into the .heating coil 24, and is -continued until the -temperature of the oil rises to a point where i the chemical or chemicals to be added to the oil are active. It vwill be understood that- I v this is done because chemicals, such as -are Laconic tures and rapidly athigher temperatures,

4and, if the temperature 1s too low, the operation will become too tedious and, if, on the other hand, the temperature vis too high,

the oil may become scorched, giving rise to objectionable odor and taste. I prefer to employ a temperature between 160 F. and

190 F., which temperature will usually be reached within an hour after steam isp-first admitted to the heating coil, but the time depends largely'upon the area of the heating coil.

While the preliminary heating of the oil is going on, the chemicals used in the treatmentof the sulfur-bearing oil may be mixed varied as conditions and qualitiesof in the tank 6 and, for this purpose, I preferably employ the following proportions, results, may be the oil but it will be understood that they may require, or may be deemed expedient,

. Nasen@ 265 peunds Caustic soda 70 pounds 'Water 458 pounds v vwater is added, the diculty 'of getting a without departing from the spirit oli-my invention.

Suld of sodav (commercial) I employ the causticsoda for threerpurposes-namely, (l) to neutralize any acid 'bodies left in the oil from previous refin-l ing. processes, (2) for the purpose of insuring alkalinity to the solution, and (3) because the solution appears to be more active inits action upon the elementary sulfur contained in the oil when decidedly alkaline. Y

More `water may be'addedthan is indicated, but a longer time will then be neces# sary to complete the operation. .If less thorough incorporation of/oil and the treating solution is increased.

,Whengthe'chemicali solution above. de-

" scribed-has'been effected, it iso about the sametemperature as theoL-namely, 160 I?.l to 190011?. and this solution .is then in.- jected into the- Oil within; the cylinder. In order to accomplish-this, the chemical. is drawn through thepipe 7 to fthe pump 8 and Vis discharged from the latter' through`A the' `pipes' 10, `11, 4and 4 perforated spray f nozzle 12, into'the oil. It -is important,

although not essential, to have thechemic'al in the pipes 10, l1 and'spray nozzle 12 under 4 pressure which'will be continuousithrough said) pipes up v-to the perorations4 inl the nozzle, so that the jets of the chemical issuing frorn'the latter will strike the oi'l with 7 considerablefforce and .effect a thorough mingling of the `oil and the chemical .solution. v

` @foil in the manner described will gradually The v.chemical solution' injectedv into the End its way by gravity through the body` valvesla, 5 and 17 closed, so that the solution, which has been partially used, will accumulate in the bottom of the agitator, and the pumping iis continued until all, or the desired amount, is drawn from the tank 6 and injected into the agitator. When vthe desired amount of chemical solution has been fed to the oil,'the valves 13a and 14 areopened and the valves 5, 9 'and 17 closed, and the pump is then operated to circulate the solution through the body of oil being treated, the pipe 13, the pump, the pipes l0, 11, and spray nozzle 12. During this circulation the temperature of the oil being treated is maintained by means of the coil 24 at a temperature of from approximately 160 F. to approximately 190 F. During thetreatment described'test samples of theJl oil are taken from time to time, said samples being washed with water and filtered through filter paper to remove the last traces of moisture, and areA then placed in a test glass with a piece of bright copper and the copper, as above described, thechemical "solution is allowed to settle in Vthe conical bottom of the vessel, and the settling is con tinued for a period of from six to ten hours inorderto insure all of the solution being separated from the treated oil. Whenthe maximum separation of the solution. is assured by adequate settling, the solution may be drawn off from the vesseland returned to the tank l6 through the pipe 4, 'the pipe l5 and the discharge 16, and said solution reserved for further use inthe treatment of o il.

Y I then treat the oil to remove therefrom Iany residual alkaline sulfid which may still besuspended in. the oil. I prefer to accomlish this by treating theoill with what is own asa still wash either by playing" water lfrom a han'dehose. onto the surface of the oil, drawing the water oil' continuously at the bottom of the vessel as the water may settle, or the water may be applied by pumpingit through a permanent spray pipe S- arranged 'at the top of the cylinder..V This treatment may be ollowed upby an injection of live steam'through the pipes 18,-19. This washing process,-including the water wash and the steam, may extend: over a period of four hours, but may be done in less or'grea'ter time', according to circumstances.

Instead' of injecting' live steam from a boiler into the base of the receptacle, I may pump clear, pure water into the bottom of the re-.

ceptacle and generate steam therefrom, wh1le'in direct contact with the oil by means of'a heating coil 24 similar to the coil 24.

f This latter method is sometimes preferable because ordinary boiler steam may contain 1mpur1t1es which will'be detrimental to 'the oilgbeing treated `The oil is then allowed -tofs'tand for about ten to twelve hours and cutting4 oli' the steam flowing through the pipes 18, 19, and injecti air from the pipe -20` into the pipes 18.an 19 and into the body of oil.A This step of the process may continue fora period of from approximately one to approximately three hours, where-l upon the oil is usually found brightand is considered finished.-

-ln employing sulfids of the .alkali metals,

it is preferable to use the same in solution, in order to obtain the best results, and4 the apparatus shown in Fig. 1, is well adapted for the application of the solution to the oili v In the above description of the method, I have described the application of an alkali metal sullid because theloil treated does not contain sulfureted hydrogen and, therefore,-

a .previously prepared sulfid must be used. Ifj-.the oil contained sulfureted hydrogen in suliicient amount, Iwould proceed by treating with a solution 4of alkali metal in the form of the hydroxid, for example, NaOH,

'in Vwhich-case the alkali metal would react with the sulfureted hydrogen to' produce the monosulfid and water, and -the monosuliid so formed would act to remove the elementar sulfur. i i5. l

stead of treating with a'solution of the previously prepared ,monosullid as devscribed, l may also treat oil not contain-ing sulfureted hydrogen, with a solution of the hydroxid, for example, NaOH, and produce he sulfid by injectmg sulfureted hydrogen into the body 'of the oil to jreact with the hydroxid of the alkali metal.

In both of these last-mentioned methods, the amounts ,'ofkohemical used z'. e. the hydroxid, are

chemically determinable in accordance with the directions heretofore given for the use of the'previously prepared mono-sulfid, and inaccordance with the amount of ILS contained in the oil,A and in case the oil contains no HzS' and the latter is to ,be supplied, the amount thereof, -and of the hydroxid necessary to roduce the required lamount of alkaline'\su f id are also determinof soda, thereby forming sulfid of lime and able in accordance with thevsaid receipts.

In Figs..2 and 3,1 show xan apparatusdfor placed preferably in an cle, into which 1s poure `a mixture of 600 'aecomo carrying out 4the `process 'with sulds of the alkaline earth metals, the form shown be ing employed because it is'preferable to use the alkaline earth metal group in the solid "forni:l 1- 'l.` his ap aratusY includes a vertically disposed cylin er or tank 30, adapted to contain the oil to be'desulfurized, a feed, 'pipe 31, enteringthe lupper portion of the 'cylinderto feed 'the oil to the latter. The cylinderis provided with an upper head '32,ahd a'lowerhe'ad33, the former being "proiided with a manhole 34. lffhe lower headis provided with a central opening 35 discharging into a neck 36, bolted to said head, and-close'd'at its lower endby a re- .moi'rajble cover plate 37. The body of the .neckis of less diameter th-an'the opening 35,

for. "apurpose to'be described, and is provided-'with an external Hlg 0r' shell 38 `forlihing -with said neckan annular passagie9, having an inclined bottoni 40, said passage being accessible to theA interior of thefcylinder through the annular space 41 'ador'ded between t e upper portion of the neck and the edge of the openingg. rlhe upper edge portion of the dange" 38 provids convenient means by which.l the neckv yao ma "Abe bolted to the cylinder. Asuitable" out et pipe 39a`leads from the passage 39.

Ylfhe bottom head of the .cylinder is .pro-

vided with a false bottom consisting o f a layer of wire mesh 42, preferably completely covering said head,.and overlying this wire 'mesh isa layer of canvas 43, or :other suitable-material, the edges of the latter extending upward for a distance about the cirvica cur'rl'iference of the lower head as at44, forl a j purpose to be presently set forth. Both the mes and the canvas covering arecut away at the content as shown, thev innerl edge of the -mesh preferably vterminatingslightly.

short of theannular passage 39whilethe inner edge of the canvasu is carried over saidV v passage and secured to said neck by a clampf mring 45 and bolts-46;(

he wall of the cylinder is provided w1th an inwardly projecting annular lange 47, l

overlyinglthe outer edges 'ofhthe canvas and wire mes layers, the space between the said flange andthe canvas being packed with cotcent its lower en j ortion the cylinder/is 800 pounds of earth groups, I proceed as freshly burned lime?. are o en pan or recepta-A ole 49 for a'purposeto l pounds of commercial suld of soda and 50 allons (417 pounds) of water. AAs thelime s acks there is a decomposition of the sulid caustic soda. .Upon the terminationof the 11h ton or wool waste aching, as at 48. -Afdja-v the filter-like bed of lime and causticsoda should be granular and somewhat coarse. The material is then placed in.; the chamber of the tank 30 and spread evenly over the false bottom thereof to the proper height, as indicated by the dotted line'in Fig. 2 of the drawings. When the material is packed in the tank the impure oil to* be desulfurized is pumped .in at the top of the tank through the pipe 31', and is permitted to percolate down through of suliid of lime. The oil in passing through the sulfid of lime is'comvpletely desulfurized by reaction of the sulfur with the sulfid of lime by simple addition to produce higher sulids, as has `beenpreviously set forth. 4The degree of desuljfurization may be determined by the copper test described on samples of the oil taken from the outlet pipe 39a. The purification in this l show no blackening of copper when-tested of the oil tends to emulsify as described, whereupon the exhausted sullid is removed and the tank is recharged with a fresh supply of sulid.

The filtering method, above described, effects .contact between the oil and 4solid sulfid as distinguished from contact of the oil and liquid suld in the alternative process. The twomethods are largely interchangeable, but the filtration method may be used when the chemical and physical character hof the oil make it appear desirwith a liquid, as for example, when a sample the water solution. The ltering process provides for a systematic use of the active agent; that is, asA the operation progresses the `raw o il comes in contact with partially exhausted sulid first, and on passing to the n. bottom of the filter it meets suld of'a less and less degree of exhaustion. If desired or necessary, I may place a layer of water- 451 moistened porous material such as burlap on the. canvas 43 beneath the suld in order to remove an odors which may be introduced by or resut from themseof the suld. The use of the water moi'stened porous material isdesirable when the 'active agent is calcium monosul'iifd prepared from suld of soda of commerceandan excess caustic soda. It

frequently happensthat the commercial sulid offsoda contains volatile sulfurous impuritie'swhich impartto the oil an unpleasant odor resembling sulfureted hydrogen which is-removed by moisture through absorption.

In the false bottom construction, the canvas supports the sulid of lime without al- -lowing 1t vto escape, while the wire mesh provides a proper space to permit the oil to liow to the outlet. Theangle-iron or flange 47 and the packing 4,8 revents leakageof the chemical employed'.- out the outer edges when treated in -the cylinder without disturbing the false bottom or injury to the same.

What I claim and desire to secure by Letters Patent of the United States is 1. The process of -removing elementary I Sulfur from petroleum oil, which consists in subjecting said oil to an alkaline sulfid.

2. The process of removing elementary sulfur from petroleum oil, which consists in subjecting said oil to an alkaline suliid and continuing the treatment until the treated oil ceases to 'have a darkening eli'ect on metallic copper. Y

3. The process of removing elementary sulfurfrom petroleum oil, which consists in treating said oil with an alkaline sulid accompanied by heat at a temperature of from 160 F. to 190 F.

4. The process of removing elementary sulfur from petroleum oil, which consists in. subjecting said oil to an alkaline suld and under alkaline conditions.

5. The process ofl removing elementary sulfur from petroleum oil, which consists in subjecting said oilfto a solution of an alkaline sulfid. f 4

6. The process of removingv elementary sulfur from petroleum oil, which consists in subjecting said oil to a solution of an v alkaline sullid, and circulating said solution able to treat the oil with a solid rather than through the body of petroleum oil.

7. TheV process of removing elementary sulfur from petroleum oil, which consists in subjecting said oil to a solution of an alkaline sulid, and circulating said solution through the body of petroleumoil until the treated oil ceases to have a darkening effect onmetallic copper.

8. The process of removing elementary sulfur from petroleum oil, which consistsin subjecting said oil to a circulating stream of a solution of alkaline sulfid and a substance insuring alkalinity ofA said solution.

9. The process of removing elementary sulfur from petroleum oil, which consists 'in subjecting said oil -to a solution of alka-l line 'sodium sulfid in the -proportion of about 2615 parts lby'weight of said suliid to about 458 parts by similar weight of water.

10. The process of removing elementary sulfur from petroleum oil, which consists in sulfur from petroleum oil, which consists in subjecting said oil to a solution of sodium sulidand caustic soda.

13; Ihe process of removing elementary sulfur from petroleum oil, which consists in subjecting said oil to asolution of alkaline sodium sulid in the proportion of approximately 265 parts `by Weight of. said sullid to approximately 458 parts by similar Weight of water to which is added a n'eutralizing agent.

14. The process of removing elementary sulfur from petroleum oil, Whichconsists in subjecting said oil to a solution of alka- 15.

line sulid and caustic soda.

15. The process of removing elementary sulfur from petroleum oil, which consists in heating said oil for approximately one hour,sub]ecting the same to a solution. of an alkaline slliid for from approximately o ne hour to approximately three hours, sep-` 1 arating the sulfid from the o1l and aftertreating the'oil to remove residual sulfld in heating suspended in the oil.

16. The process of removing elementary sulfur from petroleum oil, which consists said oil for approximately one hour, subjecting the same to a solution of an alkaline sulid for from approximately one Laconic hour to approximately three hours, While maintaining the same at a temperature of from about 160 F. to. 190 F., separating the sulfid from the 'oil and after-treating the oil to removeresidual suld suspended in the oil.

17. The process of removingelementary sulfur from petroleum oil, Which consists y .in heating said oil to a temperature of .from about 160 F. to 190 F., subjecting the same vto a solution of an alkaline suld,`separating 19. The process of removing elementary sulfur from petroleum` oil, which-consists in treatin said oil' with an alkaline sulid accompanled by agitation and heat.

.In testimony whereof I have hereunto signed my name in the presence of two subscribing Witnesses. p

ERNEST B. COBB. Witnesses:

C. G. UN, ARTHUR G. DANrmLL. 

